EP0274194B1 - Verfahren zur Herstellung von 2-Nitro-5-phenoxy-N-alkylsulfonylbenzamiden durch Nitrierung - Google Patents

Verfahren zur Herstellung von 2-Nitro-5-phenoxy-N-alkylsulfonylbenzamiden durch Nitrierung Download PDF

Info

Publication number
EP0274194B1
EP0274194B1 EP87309705A EP87309705A EP0274194B1 EP 0274194 B1 EP0274194 B1 EP 0274194B1 EP 87309705 A EP87309705 A EP 87309705A EP 87309705 A EP87309705 A EP 87309705A EP 0274194 B1 EP0274194 B1 EP 0274194B1
Authority
EP
European Patent Office
Prior art keywords
formula
compound
process according
hydrogen
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87309705A
Other languages
English (en)
French (fr)
Other versions
EP0274194A1 (de
Inventor
Colin Hardy
Tony Ronald Martin
Jerzy Czyzewski
Daniel Levin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Priority to AT87309705T priority Critical patent/ATE73765T1/de
Publication of EP0274194A1 publication Critical patent/EP0274194A1/de
Application granted granted Critical
Publication of EP0274194B1 publication Critical patent/EP0274194B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/03—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton

Definitions

  • the present invention relates to a process for preparing certain herbicidal diphenyl ether derivatives.
  • EP-A-22610 discloses a multi-stage process for preparing 2-nitro-5-(substituted phenoxy)benzoic acids and salts thereof which process includes nitration of the corresponding 5-(substituted phenoxy)benzoic acid.
  • European Patent No. 3416 discloses diphenyl ether compounds of formula (I) : and tautomers and salts thereof; wherein R1 is C 1-6 alkyl optionally substituted by one or more halogen atoms; R2 is hydrogen, fluorine, chlorine, bromine or iodine or a nitro group; R3 is hydrogen, fluorine, chlorine, bromine or iodine, C 1-6 alkyl, trifluoromethyl or a cyano group; R4 is hydrogen, fluorine, chlorine, bromine, iodine or trifluoromethyl; R5 is fluorine, chlorine, bromine, iodine or trifluoromethyl; and R6 is hydrogen or C 1-4 alkyl. Salts of formula (I) are those formed by reacting a compound of formula (II) where R6 is hydrogen with a base as described in EP 3416. Processes for the preparation of these compounds are also described.
  • a process for preparing a compound of formula (II) : or a tautomer or salt thereof in substantially pure form wherein R1, R2, R3, R4, R5 and R6 are as hereinbefore defined in relation to formula (I); which process comprises nitrating a compound of formula (III) : or a salt thereof wherein R1, R3, R4, R5 and R6 are as hereinbefore defined in relation to formula (I); in a solvent which is resistant to nitration under the desired reaction conditions and suitable for purification of the product of formula (II), heating the resultant solution to a temperature sufficient to at least partially dissolve the desired product and impurities and cooling the solution to precipitate the compound of formula (II) in substantially pure form.
  • salt of formula (II) or (III) refer to the compounds obtained by reacting the appropriate compound where R6 is hydrogen with a base to form a salt such as the sodium or potassium salt.
  • water can be added to the reaction mixture during the final purification step in order to dilute any unreacted acid present.
  • the nitration is effected by reaction with standard nitrating agent such as concentrated nitric acid, sodium nitrate, a mixture of concentrated sulphuric acid and sodium nitrate or a mixture of concentrated nitric acid and concentrated sulphuric acid.
  • standard nitrating agent such as concentrated nitric acid, sodium nitrate, a mixture of concentrated sulphuric acid and sodium nitrate or a mixture of concentrated nitric acid and concentrated sulphuric acid.
  • a salt of the compound of formula (III) such as the potassium salt is used in the reaction.
  • Suitable solvents for use in the process include halogenated alkanes in particular chlorinated hydrocarbons such as dichloromethane, dichloroethene and dichloropropane in their various isomeric forms, chlorofluorohydrocarbons such as the Arctons, and aromatic solvents which are deactivated with respect to nitration such as nitrobenzene.
  • chlorinated hydrocarbons such as dichloromethane, dichloroethene and dichloropropane in their various isomeric forms
  • chlorofluorohydrocarbons such as the Arctons
  • aromatic solvents which are deactivated with respect to nitration such as nitrobenzene.
  • the particular solvent employed will depend upon the solubility of the particular compound of formula (I) being prepared in it. The skilled chemist will be able to determine by routine procedures whether any specific solvent is appropriate for the nitration and purification steps.
  • the nitration step of the process is suitably carried out at moderate temperatures of from 0°C to 40°C and preferably at room temperature.
  • the purification stages (heating, cooling and filtering) will depend upon the solvent and the compound of formula (I) being prepared.
  • the solution is heated to a temperature such that a substantial proportion of impurites are dissolved for example more than 70% w/w. This will mean that at least partial dissolution of the product also takes place.
  • the water content of the reaction mixture is suitably controlled to an acceptable level.
  • the precise content required for optimum results will depend upon a number of factors including, for example, the content of sulphuric acid present in the nitrating agents. Generally a water content of from 1%-3% w/w has been found to be acceptable.
  • a convenient method of controlling the water content is to heat the solution to an appropriate temperature and remove water by distillation prior to adding the nitrating agent.
  • the expression "in substantially pure form” means that the product contains less than 10 % impurities, preferably less than 5 % impurities. Most preferably the product is substantially free of impurities.
  • reaction of the compound of formula (IV) with the compound of formula (V) is carried out in the same solvent as that used in the nitration and purification steps. This enables the compound salt of formula (III) to be reacted directly without first isolating it from solution.
  • Compounds of formula (IV) and (V) are either known compounds or they can be prepared from known compounds by conventional methods.
  • the process of the invention is used to prepare a compound of formula (VI) : wherein R8 is hydrogen or fluorine and R9 is methyl or ethyl.
  • R8 is hydrogen and R9 is methyl
  • a preferred solvent for use in the above described process steps is 1,2-dichloroethane.
  • R8 is fluorine and R9 is ethyl
  • a preferred solvent is 1,2-dichloropropane.
  • the concentration of the reaction mixture in the solution can be varied at each stage in the process to the optimum for that stage by adding further solvent.
  • the reaction of the appropriate compounds of formula (IV) and (V) is carried out at a concentration of about 28% w/w when the solvent is 1,2-dichloroethane.
  • the resultant solution is preferably diluted to about 21% w/w by addition of further 1,2-dichloroethane in order to effect the nitration reaction.
  • a nitrating agent comprising about 1.4 moles of the concentrated nitric acid to about 5 moles of concentrated sulphuric acid is added dropwise to the solution for every 1 mole of the compound of formula (III) present.
  • 1,2-dichloroethane is preferably added to dilute the solution to about 15% w/w (excluding any added water) for the purification step.
  • the purification is carried out by heating the solution to about 70-72°C and then cooling in a controlled manner to 20°C.
  • 1,2-dichloroethane 360ml was charged into a 21 jacketed glass reactor, followed by methane sulphonamide (74.2g) and the temperature was raised to 50°C.
  • Anhydrous potassium carbonate 210g was added with vigorous stirring and the reaction mixture was heated to reflux (83°C).
  • 5-(2-chloro-4-trifluoromethylphenoxy)-benzoyl chloride 189.73g was added over a period of 11 ⁇ 2 hours under reflux. The mixture was refluxed for a further 30 minutes, then water (420ml) added, and the temperature raised to 70°C, and maintained for a further 1 ⁇ 2 hour.
  • Example 1A A sample of the solution obtained in Example 1A (468.5g) was placed in a 500ml flask and a mixture of concentrated sulphuric acid (86.4g) and a mixture of a concentrated nitric acid (23.7g) and concentrated sulphuric acid (48.1g) was added over a period of 2 hours with stirring, the temperature being maintained at 35°C throughout.
  • the reaction mixture was then allowed to cool to ambient temperature for 90 minutes after which water (370ml) and 1,2-dichloroethane (100ml) were added.
  • the mixture was heated under reflux (75°C) for 30 minutes and allowed to cool to 20°C overnight during which time solid product precipitated.
  • the solid was filtered off, washed with water and dried at 80°C to give the desired product (72g at 93% purity).
  • This Example illustrates the preparation of the compound of formula:
  • An aqueous solution (145.8g) of the potassium salt of 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-N-ethanesulphonylbenzamide (34.3g) was placed in a glass vessel and 1,2-dichloropropane (92.5g) added.
  • the mixture was heated gradually to 70-75°C with stirring and 50% aqueous sulphuric acid was added dropwise until the pH of the aqueous phase was 1.
  • the mixture was allowed to settle and the organic phase separated off.
  • This Example illustrates the preparation of the compound of Example 1.
  • a 25% w/w aqueous solution (400g) of the potassium salt of 5-(2-chloro-4-trifluoromethylphenoxy)-N-methanesulphonylbenzamide, 1,2-dichloroethane (614g) and a 1:2 mixture of concentrated nitric acid and concentrated sulphuric acid (21.2g) were placed in a reactor vessel and ortho-phosphoric acid (40g) added dropwise until the pH was 1.6.
  • the mixture was heated to 70°C and allowed to settle, after which the organic phase was separated off.
  • the organic phase was heated to a temperature of 86°C, with azeotropic removal of water by distillation.
  • This solution (532.1g) was placed in a reaction vessel and concentrated sulphuric acid (54 g) and a 1:2 mixture (52.35g) of concentrated nitric and concentrated sulphuric acid was added dropwise over a period of 1 hour 50 minutes during which time the temperature was maintained at 35°C.
  • the mixture was then transferred to a separate vessel with the addition of 1,2-dichloroethane (12ml) and after stirring for 2 hours at 35°C, water (363g) was added. Following heating to a temperature of 73°C, the mixture was allowed to cool slowly to 27°C whereupon the desired product was formed as a precipitate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Claims (10)

  1. Verfahren zur Herstellung einer Verbindung der Formel II
    Figure imgb0019
     und von Tautomeren und Salzen davon in im wesentlichen reiner Form, worin R¹ für C₁₋₆-Alkyl steht, das gegebenenfalls durch ein oder mehrere Halogenatome substituiert ist, R³ für Wasserstoff, Fluor, Chlor, Brom, Jod, C₁₋₆-Alkyl, Trifluoromethyl oder Cyano steht, R⁴ für Wasserstoff, Fluor, Chlor, Brom, Jod oder Trifluoromethyl steht, R⁵ für Fluor, Chlor, Brom, Jod oder Trifluoromethyl steht und R⁶ für Wasserstoff oder C₁₋₄-Alkyl steht, bei welchem Verfahren eine Verbindung der Formel III
    Figure imgb0020
     oder ein Salz davon, worin R¹, R³, R⁴, R⁵ und R⁶ die oben angegebenen Bedeutungen besitzen, mit einem Nitrierungsmittel in einem Lösungsmittel, das gegenüber einer Nitrierung unter den herrschenden Reaktionsbedingungen beständig ist und sich für die Reinigung des Produkts der Formel II eignet, nitriert wird, die erhaltene Lösung auf eine Temperatur erhitzt wird, die ausreicht, das gewünschte Produkt und Verunreinigungen zumindest teilweise aufzulösen, und die Lösung abgekühlt wird, um die Verbindung der Formel II in im wesentlichen reiner Form auszufällen.
  2. Verfahren nach Anspruch 1 , bei welchem das Lösungsmittel ausgewählt wird aus halogenierten Alkanen, Fluorkohlenwasserstoffen und aromatischen Lösungsmitteln, die gegenüber einer Nitrierung deaktiviert sind.
  3. Verfahren nach Anspruch 1 und 2, bei welchem ein Salz einer Verbindung der Formel III verwendet wird.
  4. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem die Nitrierung durch Umsetzung mit einem Nitrierungsmittel ausgeführt wird, das ausgewählt wird aus konzentrierter Salpetersäure, Natriumnitrat, einem Gemisch von konzentrierter Schwefelsäure und Natriumnitrat oder einem Gemisch von konzentrierter Salpetersäure und Schwefelsäure.
  5. Verfahren nach einem der vorhergehenden Ansprüche zur Herstellung einer Verbindung der Formel VI,
    Figure imgb0021
     worin R⁸ für Wasserstoff oder Fluor steht und R⁹ für Methyl oder Ethyl steht.
  6. Verfahren nach Anspruch 5, bei welchem die Verbindung der Formel VI eine solche ist, worin R⁸ für Wasserstoff steht und R⁹ für Methyl steht, und bei welchem als Lösungsmittel 1,2-Dichloroethan verwendet wird.
  7. Verfahren nach Anspruch 5, bei welchem die Verbindung der Formel VI eine solche ist, worin R⁸ für Fluor steht und R⁹ für Ethyl steht, und bei welchem als Lösungsmittel 1,2-Dichloropropan verwendet wird.
  8. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem die Verbindung der Formel III dadurch hergestellt wird, daß eine Verbindung der Formel IV,
    Figure imgb0022
     worin R³, R⁴ und R⁵ die in Anspruch 1 angegebenen Bedeutungen besitzen und R⁷ für eine abspaltbare Gruppe steht, mit einer Verbindung der Formel V,
    Figure imgb0023
     worin R¹ und R⁶ die in Anspruch 1 angegebenen Bedeutungen besitzen, in Gegenwart einer Base und im genannten Lösungsmittel umgesetzt wird.
  9. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem der Wassergehalt des anfänglichen Reaktionsgemischs auf 1 bis 3 Gew.-% eingestellt wird.
  10. Verfahren nach Anspruch 9, bei welchem der Wassergehalt dadurch eingestellt wird, daß das Reaktionsgemisch auf eine geeignete Temperatur erhitzt wird und Wasser vor der Zugabe des Nitrierungsmittels durch Destillation entfernt wird.
EP87309705A 1986-11-25 1987-11-03 Verfahren zur Herstellung von 2-Nitro-5-phenoxy-N-alkylsulfonylbenzamiden durch Nitrierung Expired - Lifetime EP0274194B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87309705T ATE73765T1 (de) 1986-11-25 1987-11-03 Verfahren zur herstellung von 2-nitro-5-phenoxy-n-alkylsulfonylbenzamiden durch nitrierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8628109 1986-11-25
GB868628109A GB8628109D0 (en) 1986-11-25 1986-11-25 Chemical process

Publications (2)

Publication Number Publication Date
EP0274194A1 EP0274194A1 (de) 1988-07-13
EP0274194B1 true EP0274194B1 (de) 1992-03-18

Family

ID=10607873

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87309705A Expired - Lifetime EP0274194B1 (de) 1986-11-25 1987-11-03 Verfahren zur Herstellung von 2-Nitro-5-phenoxy-N-alkylsulfonylbenzamiden durch Nitrierung

Country Status (13)

Country Link
US (1) US4845285A (de)
EP (1) EP0274194B1 (de)
JP (1) JP2502327B2 (de)
KR (1) KR950013107B1 (de)
AR (1) AR243867A1 (de)
AT (1) ATE73765T1 (de)
AU (1) AU620022B2 (de)
BR (1) BR8706322A (de)
DE (1) DE3777596D1 (de)
GB (2) GB8628109D0 (de)
HU (1) HU203714B (de)
IL (1) IL84403A (de)
ZA (1) ZA878326B (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6028219A (en) * 1995-09-13 2000-02-22 Zeneca Limited Process for the nitration of diphenylethers
GB9518704D0 (en) 1995-09-13 1995-11-15 Zeneca Ltd Chemical process
US5910604A (en) * 1995-09-13 1999-06-08 Zeneca Limited Purification process
GB9930369D0 (en) 1999-12-22 2000-02-09 Zeneca Ltd Chemical process
CN102030655B (zh) * 2010-10-21 2013-03-27 上虞颖泰精细化工有限公司 二苯醚衍生物的合成方法以及乙氧氟草醚的合成方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856895A (en) * 1968-10-04 1974-12-24 F Eiseman Phosphonamides
US4005102A (en) * 1974-07-08 1977-01-25 General Electric Company Process for making 4-nitro-n-methylphthalimide
GR65995B (de) * 1978-01-19 1981-01-13 Ici Ltd
DE2960664D1 (en) * 1978-01-19 1981-11-19 Ici Plc Diphenyl ether compounds useful as herbicides; methods of using them, processes for preparing them, and herbicidal compositions containing them
DE3071736D1 (en) * 1979-06-22 1986-10-09 Rhone Poulenc Agrochimie Process for preparing 2-nitro-5-(substituted-phenoxy) benzoic acids and salts thereof
US4465508A (en) * 1979-07-18 1984-08-14 Imperial Chemical Industries Plc Diphenyl ether herbicides
US4388472A (en) * 1979-07-18 1983-06-14 Imperial Chemical Industries Plc Substituted diphenyl ethers
DE3165721D1 (en) * 1980-02-05 1984-10-04 Ici Plc Method of preparing fluorine-substituted diphenyl ether derivatives and fluorine-substituted halogeno benzene derivatives for use therein
FR2510105A1 (fr) * 1981-07-27 1983-01-28 Rhone Poulenc Agrochimie Procede de preparation d'acides phenoxybenzoiques
FR2524465A1 (fr) * 1982-04-01 1983-10-07 Rhone Poulenc Agrochimie Nouveaux herbicides derives d'acides phenoxybenzoiques a groupe sulfonimide
GB8309648D0 (en) * 1983-04-08 1983-05-11 Ici Plc Herbicidal compounds

Also Published As

Publication number Publication date
GB8725672D0 (en) 1987-12-09
ATE73765T1 (de) 1992-04-15
HUT45957A (en) 1988-09-28
EP0274194A1 (de) 1988-07-13
IL84403A (en) 1992-05-25
JP2502327B2 (ja) 1996-05-29
AU8133487A (en) 1988-05-26
KR880006179A (ko) 1988-07-21
JPS63141958A (ja) 1988-06-14
KR950013107B1 (ko) 1995-10-24
ZA878326B (en) 1988-05-25
HU203714B (en) 1991-09-30
GB8628109D0 (en) 1986-12-31
BR8706322A (pt) 1988-07-19
DE3777596D1 (de) 1992-04-23
AU620022B2 (en) 1992-02-13
US4845285A (en) 1989-07-04
AR243867A1 (es) 1993-09-30

Similar Documents

Publication Publication Date Title
EP0055951B1 (de) Verfahren zur Herstellung von Anthrachinon und dessen substituierten Derivaten
JP2001518904A (ja) ４−ブロモメチルジフェニル化合物の調製方法
EP0208948B1 (de) Verfahren zur optischen Spaltung eines Phenylessigsäurederivats
EP0274194B1 (de) Verfahren zur Herstellung von 2-Nitro-5-phenoxy-N-alkylsulfonylbenzamiden durch Nitrierung
EP1000010B1 (de) Nitrierungsverfahren zur herstellung von diphenylethern
JPS5838235A (ja) フエノキシ安息香酸誘導体の精製方法
JP2003335735A (ja) パーフルオロイソプロピルアニリン類の製造方法
EP1451140A1 (de) Neues verfahren
JP2005532406A (ja) ニトロフェノールの製造方法
UA73329C2 (uk) N-(4,5-бісметансульфоніл-2-метилбензоїл)гуанідину гідрохлорид та спосіб його одержання
KR0152518B1 (ko) 히드록실아민 유도체
JPH0354930B2 (de)
JPH0761993B2 (ja) アジドスルホニル安息香酸の製造法
JPS59137429A (ja) 核ハロゲン化３−フルオロトルエン類とその製造方法
JP2003518088A (ja) ジフェニルエーテル化合物の製造方法
JPH0811745B2 (ja) ３−アミノ−４−ヒドロキシ安息香酸の製造方法
JP3089373B2 (ja) ２−メルカプト−フェノチアジンの製造方法
JPH0258253B2 (de)
JPH10158206A (ja) １，１，１−トリス（４−ヒドロキシフェニル）アルカンの精製法
JP2648346B2 (ja) ハロゲノイサト酸無水物の製法
JPS6054948B2 (ja) α，β↓−不飽和環状脂肪族ケトキシムから芳香族アミンを製造する方法
JP3927835B2 (ja) ヨウ化芳香族化合物ジアセテートの製造方法
CN114364655A (zh) 硝酸α-甲基-[4-(硝基)-2-(三氟甲基)]-苄酯的制备方法
JPH04208270A (ja) フェノチアジンの２位に直接メルカプト基を導入する　方法
JP3244622B2 (ja) ベンザンスロンの臭素化方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19881209

17Q First examination report despatched

Effective date: 19900823

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19920318

Ref country code: NL

Effective date: 19920318

Ref country code: LI

Effective date: 19920318

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19920318

Ref country code: CH

Effective date: 19920318

Ref country code: BE

Effective date: 19920318

Ref country code: AT

Effective date: 19920318

REF Corresponds to:

Ref document number: 73765

Country of ref document: AT

Date of ref document: 19920415

Kind code of ref document: T

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 3777596

Country of ref document: DE

Date of ref document: 19920423

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19920629

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19921130

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19991103

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19991108

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19991109

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001103

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20001103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051103